EP2768924A1 - Utilisation de dérivés de tris(2-hydroxyphényl)méthane pour la récupération tertiaire de pétrole - Google Patents

Utilisation de dérivés de tris(2-hydroxyphényl)méthane pour la récupération tertiaire de pétrole

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Publication number
EP2768924A1
EP2768924A1 EP12775219.4A EP12775219A EP2768924A1 EP 2768924 A1 EP2768924 A1 EP 2768924A1 EP 12775219 A EP12775219 A EP 12775219A EP 2768924 A1 EP2768924 A1 EP 2768924A1
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EP
European Patent Office
Prior art keywords
tris
hydroxyphenyl
groups
radicals
methane
Prior art date
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Granted
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EP12775219.4A
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German (de)
English (en)
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EP2768924B1 (fr
Inventor
Guenter Oetter
Bjoern Heinz
Markus Hansch
Horst Weiss
Peter Deglmann
Vandana Kurkal-Siebert
Frank Heilmann
Ravindra Aglave
Lorenz Siggel
Benjamin Wenzke
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Wintershall Dea GmbH
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Wintershall Holding GmbH
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Priority to EP12775219.4A priority Critical patent/EP2768924B1/fr
Publication of EP2768924A1 publication Critical patent/EP2768924A1/fr
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Publication of EP2768924B1 publication Critical patent/EP2768924B1/fr
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/10—Polyhydroxy benzenes; Alkylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/30—Viscoelastic surfactants [VES]

Definitions

  • the present invention relates to the use of tris (2-hydroxyphenyl) methane derivatives for tertiary petroleum production.
  • a subject matter of the invention is also a process for mineral oil production in which an aqueous formulation is used which contains at least one tris (2-hydroxyphenyl) methane derivative, which is passed through at least one injection well into a crude oil deposit, for example with a reservoir. Temperature of 10 ° C to 150 ° C, is injected, and the deposit through at least one production well, the crude oil takes.
  • the secondary production may be used, in which, in addition to the wells which are used to extract the oil, the so-called production wells, further boreholes are drilled into the oil-bearing formation.
  • the so-called production wells water is injected into the reservoir (the so-called "water flooding") to maintain or increase the pressure.
  • water flooding water is injected into the reservoir (the so-called "water flooding") to maintain or increase the pressure.
  • tertiary oil recovery also known as “Enhanced Oil Recovery”, EOR
  • EOR Enhanced Oil Recovery
  • An overview of tertiary oil production using chemicals can be found, for example, in an article by DG Kessel from 1989 (Journal of Petroleum Science and Engineering, 2 (1989), 81 to 101
  • One of the known techniques of tertiary mineral oil production is the so-called “polymer flooding", in which an aqueous solution of a thickening polymer is injected through the injection bores into the crude oil deposit, the viscosity of the aqueous polymer solution being adapted to the viscosity of the crude oil.
  • polymer flooding in which an aqueous solution of a thickening polymer is injected through the injection bores into the crude oil deposit, the viscosity of the aqueous polymer solution being adapted to the viscosity of the crude oil.
  • a polymer solution it is also possible to use aqueous solutions with non-polymeric thickeners.
  • Thickeners are chemicals that increase the viscosity of aqueous solutions through to gelation. By injecting a thickened solution, the oil is forced through the cavities in the formation from the injection bore towards the production bore, and the petroleum can be pumped through the production well.
  • the fact that a thickener formulation has about the same mobility as crude oil reduces the risk that the formulation breaks through without any effect on the production bore ("fingering") .
  • the mobilization of the oil can be much smoother and more efficient than with the use of low-viscosity water by avoiding the "fingering" that occurs when using water.
  • a piston-like displacement of the oil is achieved by adjusting the mobility. As a result, the promotion of mobile oil in terms of water flow is accelerated.
  • tertiary oil production also uses surfactants in addition to thickeners. Surfactants are used in petroleum production to lower oil-water interfacial tension to very low levels, thus mobilizing additional petroleum that would otherwise remain in the rock.
  • viscoelastic surfactants can also be used for the abovementioned combination of sequentially switched “surfactant flooding” and “polymer flooding.” These viscoelastic surfactants are surface-active substances which form associates in solution which increase the viscosity of the solution.
  • associates which can form surfactants, also called micelles, form due to hydrophobic interactions.
  • the thickening properties of such solutions can usually be removed by shear, in which the associates disintegrate into smaller fragments. In this process, however, no chemical bonds are broken and the associates re-form their thickening effect in the absence of shear.
  • An object of the invention is to provide a method for oil production, which can be carried out inexpensively and technically not expensive, and which can also be used in saline oil deposits.
  • high salt contents eg at least 10,000 ppm, often at least 20,000 ppm, in particular at least 50,000 ppm
  • synthetic thickeners other than polymeric thickeners in tertiary mineral oil production.
  • non-polymeric derivatives of tris (2-hydroxyphenyl) methanes which are used according to the invention and have polyalkoxy groups or polyalkoxy groups modified with terminal hydrophilic groups as functional groups act as highly active surfactants or thickeners, even at elevated temperatures and / or high salinity ,
  • the trishydroxyphenylmethane compounds are used as complexing agents for zinc and alkali metal ions.
  • M. B. Dinger and M. J. Scott, (Eur. Org. Chem. 2000, 2467 to 2478) further describe the further reaction of the OH group of tris (3,5-dialkyl-2-hydroxyphenyl) methanes.
  • the OH functions can be derivatized by reaction with halo-carboxylic acid esters and hydrolysis and / or further reactions.
  • MB Dinger and Scott describe, for example, tris (3,5-di-t-butyl-2-carboxy-methoxyphenyl) methane, tris (3,5-di-he / f butyl-2 - [(dimethylamido) methoxy] phenyl) methane, tris ⁇ 3,5-di-ie, f-butyl-2 - [/ V- (methylglycyl) carbonylmethoxy] phenyl ⁇ methane and tris (3, 5-di-Fe / F-butyl-2 - [(benzylamino-carbonyl) -methoxy] -phenyl) -methane.
  • the derivatives can each be used as complexing agents, for example for Zn (II) ions.
  • Tris - (3,5-dialkyl-2-hydroxyphenyl) -methanes namely tripodal diglycolamides and their use for the complexation and separation of lanthanides.
  • Tris (3,5-dialkyl-2-hydroxyphenyl) methanes in which the OH group is etherified with ⁇ -amino or cyanoalkyl groups are used as intermediate in the synthesis.
  • Mitra (Dalton Trans., 2007, 3924-3935) describes particular tris (2-hydroxyphenyl) methane derivatives having terminal 2-pyridylmethylpiperazine groups. These molecules can bind zinc ions and are used as catalysts for phosphate diester synthesis. As an intermediate in the multistage synthesis, tris [2- (2-hydroxylethoxy) -3-methyl-5-t-butylphenyl] methane is disclosed.
  • EP-A-0 597 806 discloses cyclohexyl group-containing glycidyl ethers for use as reactive diluents, flexibilizers or adhesion improvers.
  • various tris (2-hydroxyphenyl) methanes are described, including those in which the OH function is etherified with a (substituted) 2-hydroxyethyl group.
  • US 2009/0155714 discloses compositions for the production of photoresists.
  • various tris (2-hydroxyphenyl) methane derivatives are used in which the OH function is esterified in each case with different carboxylic acids.
  • Surfactant micelles which form viscoelastic networks, are very stable in time before they break up into individual fragments and reform again so that the micellar network can resist shear of the surfactant solution and thus react both viscous and elastic. Further details on viscoelastic, vermiform micelle-forming surfactants such as hexadecyltrimethylammonium p-toluenesulfonate or cetylpyridinium salicylate are described, for example, in H. Hoffmann et al. (Adv. Colloid Interface Sci. 1982, 17, 275-298) or MR Rojas (Journal of Colloid and Interface Science 342 (2010) 103-109)).
  • viscoelastic surfactants are particularly suitable as thickeners and can be used in various fields of technology.
  • US 2005/0155762 discloses betaines having alkyl chains of 14 to 24 carbon atoms, for example oleyl amidopropyl betaine or erucyl amido-propyl betaine as thickening, viscoelastic surfactants.
  • these betaines have technical disadvantages, for example with regard to their stability.
  • No. 7,461,694 discloses zwitterionic surfactants having alkyl chains of 16 to 24 carbon atoms as viscoelastic surfactants.
  • WO 2008/100436 discloses a viscoelastic surfactant mixture of cationic, anionic or zwitterionic surfactants and a polymer.
  • the surfactants have alkyl chain lengths of 12 to 25 carbon atoms.
  • surfactants with long alkyl chains are used to form viscoelastic surfactant solutions.
  • a disadvantage of long alkyl chain viscoelastic surfactants is that they solubilize on contact with non-polar liquids, thereby converting the worm-like micelles into spherical aggregates and losing viscoelasticity.
  • these viscoelastic surfactants in contact with other surfactants usually form mixed micelles, whereby the viscoelasticity may also be lost.
  • Structures with short alkyl chains or structures that deviate from the usual linear construction principle of the surfactants usually form spherical micelles or only short anisometric aggregates and thus no viscoelastic surfactant solutions.
  • Known viscoelastic surfactants are often cationic surfactants, such as hexadecyltrimethylammonium p-toluenesulfonate or cetylpyridinium salicylate.
  • Cationic surfactants with long alkyl radicals are ecotoxicologically questionable (see, eg, Versteeg et al., Chem 24 (1992) 641).
  • they adsorb well to surfaces because of their positive charge, they also lose some of their effectiveness in some applications. Therefore There is a need for surfactants with a more favorable ecotoxicological profile and less tendency to adsorb.
  • the invention relates to a process for the extraction of crude oil, in which an aqueous formulation containing at least one derivative of tris- (2-hydroxyphenyl) - methane of the general formula (I) injected through at least one injection well in a Erdöllager Maschinen and the deposit by at least a production well takes the crude oil,
  • R independently of each other 0 to 4, preferably 1 to 2,
  • R 1 is a radical selected from the group of H, OH, F, Cl, Br, I,
  • R 2 independently of one another radicals of the general formula (III),
  • n is a number from 1 to 50, preferably 8 to 35, and
  • radicals R 5 are independently selected from the group of radicals R 7 , R 8 and R 9 , preferably from the group R 7 and R 8 , CH CH ⁇ -
  • R 7 R 8 R 9 where R °, X, R 10 and R j "11 independently of one another have the following meanings: a single bond or an alkylene group having 1 to 10 carbon atoms, which may optionally have functional groups as substituents,
  • H or a C 1 to C 6 hydrocarbon radical, preferably H or methyl, is a group - (R 5 -O-) m -R 6 -X, where m is a number from 0 to 50, and wherein the total number z of all groups R 5 in a radical R 2 is 1 to 50, preferably 8 to 35, with the proviso that the number z is a number from 2 to 50 if at least one X is H.
  • These compounds are chemically and thermally stable, storable over a long period of time and can also be used in salt-containing water at higher temperatures.
  • the invention also relates to a process for the extraction of crude oil, in which an aqueous formulation is used which contains, in addition to water, at least one derivative of tris (2-hydroxyphenyl) methane of the general formula (II),
  • R 1 and R 2 have the abovementioned meanings and R 3 and R 4 independently of one another are H or a C 1 to C 30 hydrocarbon radical, in particular a C 1 to C 6 hydrocarbon radical, preferably a branched C 4 radical in particular t - Butyl rest.
  • the invention also relates to a process in which a compound of the formula (II) is used in which all R 3 and R 4 are independently straight-chain or branched aliphatic C to C 6 hydrocarbon radicals, in particular t-butyl radicals ,
  • the invention also relates to a process in which X is in each case an acidic group selected from carboxyl groups -COOM, sulfonic acid groups -SO 3 M, sulfate groups -OSO 3 M, phosphonic acid groups -PO 2 M 2 or phosphoric acid groups - OPO 3 M2 where M is H + or a k-valent counterion V k Y k + , in particular Na, K or ammonium ions.
  • X is in each case an acidic group selected from carboxyl groups -COOM, sulfonic acid groups -SO 3 M, sulfate groups -OSO 3 M, phosphonic acid groups -PO 2 M 2 or phosphoric acid groups - OPO 3 M2 where M is H + or a k-valent counterion V k Y k + , in particular Na, K or ammonium ions.
  • each X is an acidic group selected from carboxyl groups -COOM, sulfonic acid groups -SO 3 M or sulfate groups -OSO 3 M, where M is H + or an alkali metal or alkaline earth metal Counterion stands.
  • the invention also relates to a process wherein the radicals R 5 are groups R 7 and / or R 8 .
  • the invention also relates to a process in which the derivatives of tris (2-hydroxyphenyl) methane used have an average molecular weight of 2,000 to 3,000 g / mol and in that the three (2-hydroxyphenyl) groups have the same structures.
  • the invention also relates to a method in which the temperature of the Erdöllager Too 10 to 150 ° C, in particular 10 to 120 ° C, often 10 to 90 ° C.
  • the invention also relates to a process in which the aqueous formulation contains as further component at least one salt in an amount of 10,000 ppm to 350,000 ppm.
  • the invention also relates to a process in which the oil production from deposits with very high salt contents and a storage temperature of 10 ° to 150 ° C takes place, the deposit in addition to petroleum and reservoir water with a salinity of 10,000 ppm to 350,000 ppm, often from 20,000 ppm to 350,000 ppm, more particularly from 100,000 ppm to 350,000 ppm, and the petroleum oil has a viscosity (measured at reservoir temperature) of at least 3 mPa * s by reacting an aqueous formulation comprising at least one derivative of tris (2 hydroxyphenyl) -methane of the formula (I) or of the formula (II) by injecting at least one injection well into the oil reservoir and withdrawing crude oil from the deposit through at least one production well, the process comprising at least the following process steps:
  • aqueous formulation of the tris- (2-hydroxyphenyl) -methane component (s) by diluting the concentrate (K) provided according to step (1) in situ with water to a concentration of 0.01 g / l to 10 g / l, preferably and from 0.05 g / l to 5 g / l,
  • the invention also relates to a process wherein the (at least one) employed derivative of tris (2-hydroxyphenyl) methane is an unbranched derivative and the concentration of the tris (2-hydroxyphenyl) methane derivative in the Formulation of 0.01 g / l to 10 g / l, preferably 0.05 g / l to 5 g / l.
  • An object of the invention is also the use of a tris (2-hydroxyphenyl) methane derivative of the formula (I) or the formula (II) as described above as a thickener, in particular as a viscoelastic thickener, in an aqueous formulation for crude oil production.
  • the invention also relates to an aqueous formulation (eg as a concentrate or ready-to-use composition) comprising as components: 0.001 to 99% by weight of at least one tris (2-hydroxyphenyl) methane derivative of the formula (I) according to Claim 1,
  • the invention also relates to an aqueous formulation comprising:
  • auxiliary component from the group of surfactants, antioxidants and biocides, and water and optionally other solvents.
  • an aqueous solution of the derivative (I) is injected through a well (the so-called injection well) into a petroleum deposit, where the mobility of the solution under formation conditions should approximate the mobility of the petroleum.
  • Suitable thickeners for flooding must therefore have the thickening effect even under the conditions of the crude oil deposit, ie also at temperatures above room temperature and in the presence of strongly saline formation water.
  • Formation waters may contain up to 35% by weight of salts.
  • the salts are, for example, alkali metal salts but also alkaline earth metal salts. Formation temperatures can be up to 150 ° C.
  • Another object of the invention is to provide a method of flooding petroleum deposits which achieves satisfactory results even at higher formation temperatures and / or high salt contents.
  • an aqueous formulation comprising at least one tris (2-hydroxyphenyl) methane derivative is injected through at least one injection well into a crude oil deposit and the crude oil is removed from the deposit by at least one production well.
  • the amount of the tris (2-hydroxyphenyl) methane derivative in the formulation is preferably from 0.01 to 10% by weight, often also from 0.05 to 10% by weight (based on the total formulation).
  • the aqueous formulation further comprises salts in an amount of 10,000 ppm to 350,000 ppm.
  • the invention can be specified as follows: Substituted tris (2-hydroxyphenyl) -methane derivatives
  • an aqueous formulation of at least one tris (2-hydroxyphenyl) methane derivative is used and injected through an injection well into a crude oil deposit.
  • the compounds used according to the invention are derivatives of tris (2-hydroxyphenyl) methane of the general formula (I).
  • the radical R 1 is a radical selected from the group of H, OH, F, Cl, Br, I, or straight-chain, branched or cyclic, aliphatic and / or aromatic C 1 to C 30 hydrocarbon groups. It is preferably H, Cl, a straight-chain or branched C to C 2 alkyl group or a benzyl group. Most preferably R 1 is H.
  • the three phenyl rings can each be substituted in the 3, 4, 5 and 6 positions independently of one another by hydrocarbon radicals R having 1 to 30 carbon atoms, it being possible for the groups to be arranged as desired. It is preferably 1 or 2 groups R per phenyl ring.
  • the groups R may be straight-chain, branched or cyclic, aliphatic and / or aromatic hydrocarbon radicals. Preferably, it is preferably straight-chain, branched or cyclic aliphatic hydrocarbon groups having 1 to 20, particularly preferably 1 to 12 carbon atoms.
  • R groups examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-propyl, t-butyl, n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl , 3-methylbutyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl, adamantyl or benzyl groups.
  • the group tert-butyl is particularly suitable.
  • the compounds used according to the invention preferably have the general formula
  • R 3 and R 4 are each independently H or hydrocarbon radicals having 1 to 30 C atoms, preferably 1 to 20 C atoms, particularly preferably 1 to 12 C atoms.
  • the hydrocarbon radicals may be straight-chain, branched, cyclic, aliphatic and / or aromatic.
  • Preferred are straight-chain, branched or cyclic aliphatic hydrocarbon groups having 1 to 20, particularly preferably 1 to 12 carbon atoms and very particularly preferably straight-chain or branched aliphatic hydrocarbon radicals having 1 to 6 carbon atoms.
  • hydrocarbyl groups examples include methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 3-methylbutyl , Hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl or adamantyl groups.
  • the radicals R 3 and R 4 are preferably H or methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-pentyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 3-methylbutyl, 1,1,3,3-tetramethylbutyl, more preferably t-butyl groups.
  • R 3 or R 4 is not H, particularly preferred in this embodiment, R 3 is not H. Most preferably, both R 3 and R 4 are not H.
  • Preferred, especially Preferred and very particularly preferred combinations of radicals R 3 and R 4 are mentioned in the following Tables 1, 2 and 3: TABLE 1 List of preferred combinations of substituents
  • both R 3 and R 4 are tert-butyl radicals.
  • radicals R 2 in the abovementioned formulas (I) and (II) are, independently of one another, radicals of the general formula
  • radicals R 5 in formula (III) are, independently of one another, groups selected from the group of radicals R 7 , R 8 and R 9
  • radicals R 10 independently of one another are H or a hydrocarbon radical having 1 to 6 carbon atoms, preferably an aliphatic hydrocarbon radical having 1 to 6 carbon atoms.
  • the alkylene group may also be incorporated in inverse orientation - CH (R 10 ) -CH 2 - in the polyoxyalkylene chain.
  • the formula (III) is intended to include both orientations, it being understood that both orientations may be contained in a chain.
  • radicals R 10 include H and also methyl, ethyl, n-propyl or phenyl radicals.
  • R 10 is H, methyl, ethyl or n-propyl radicals, preferably H, methyl or ethyl radicals, more preferably H or methyl.
  • the groups R 11 are groups of the general formula - (R 5 -O-) m -R 6 -X, where m is a number from 0 to 50.
  • m a number from 0 to 50.
  • it may be a group -R 6 -X which is directly linked to the oxygen atom, or (in the case m> 0) a group in which -R 6 -X is linked to the O atom via a polyalkoxy group.
  • R 11 may again contain groups R 8 and R 9 , the groups R 2 may also be branched several times.
  • radicals R 7 , R 8 and R 9 can be arranged as desired in the radicals R 2 , for example randomly, in blocks, alternately or with a gradient.
  • Preferred compounds of the formula (I) or (II) are structures having pure ethylene oxide chains with average chain lengths between 6-15 EO units. Also particularly preferred are EO-glycidol copolymers having 6-12 EO units and 1-5 glycidol units. Of these, copolymers having a block copolymer structure are particularly suitable.
  • X is H or a hydrophilic group.
  • a hydrophilic group comprises one or more oxygen atoms.
  • Hydrophilic groups may, in particular, be acidic groups, preferably a group selected from the group of carboxyl groups -COOM, sulfonic acid groups -SO 3 M, sulfate groups -OSO 3 M, phosphonic acid groups -PO 2 M 2 or phosphoric acid groups -OPO 3 M2, where M is H + or a k-valent counterion V k Y k + .
  • the acidic groups can therefore be present as free acid and / or as a salt thereof.
  • M is H + , it is preferably a monovalent counterion, such as NH 4 + , ammonium ions with organic radicals or alkali metal ions.
  • Preferred acidic groups are those selected from the group of carboxyl groups -COOM, sulfonic acid groups -SO 3 M or sulfate groups -
  • OSO 3 M more preferably sulphate groups -OSO 3 M.
  • Preferred hydrophilic groups furthermore include radicals which comprise at least one, preferably at least 2, OH groups, in particular monosaccharide or oligosaccharide radicals, preferably monosaccharide radicals. It can in principle be all kinds of saccharides. Preference is given to using radicals derived from pentoses and hexoses, in particular from hexoses. Examples of suitable monosaccharides include glucose, mannose, galactose, fructose or ribose. Preferably, glucose-derived radicals can be used. They may also be derivatives of the saccharides, for example products resulting from the reduction or oxidation of the saccharides. In particular, such derivatives may be sugar acids such as gluconic acid.
  • hydrophilic groups examples include, for example, amine oxide groups.
  • R 6 is a single bond or an alkylene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, which may optionally have functional groups as substituents, in particular an OH group.
  • groups include -CH 2 -, -CH 2 CH 2 -, -CH 2 -CH 2 -CH 2 - or -CH 2 -CH (OH) -CH 2 groups.
  • the total number of all groups R 5 in a radical R 2 ie the groups R 5 in the main group as well as the groups R 5 in any branches present, shall be described below z be designated. In the case of a linear group R 2 , z corresponds to the number n.
  • z is a number from 2 to 50 in the case where at least one X is H, and it is a number from 1 to 50 in the case where X is not H.
  • the numbers z, n and m relate in a known manner to the average value of the alkoxy groups present in the molecule, the mean value of course not having to be a natural number but can also be a positive rational number.
  • z, independently of the nature of the substituent X is a number from 2 to 50, in particular 4 to 40, preferably 5 to 30, particularly preferably 8 to 20 and very particularly preferably 10 to 15.
  • At least one of the radicals R 5 is a radical R 7 .
  • all radicals R 5 are radicals R 7 .
  • the radicals R 7 comprise different radicals R 10 , these can be arranged in any desired manner, for example randomly, blockwise, alternately or with a gradient.
  • at least a portion of the z radicals R 10 is H, in particular at least 20%, preferably at least 50%, particularly preferably at least 80%, and very particularly preferably all radicals R 10 are H.
  • the radicals R 2 are groups - (R 7 -O-) n -R 6 -X (IIIa). Residues R 8 and R 9 are not present in this embodiment.
  • n is a number from 5 to 30, particularly preferably from 8 to 20 and very particularly preferably from 10 to 15.
  • the radicals R 2 are groups - (- CH 2 -CH (R 12 ) -O-) a - (- CH 2 -CH 2 -O-) b -H (Nie ), with the two blocks arranged in this order. Again, this is an embodiment in which only R 7 groups are present, X is H, and R 6 is a single bond.
  • the radicals R 12 in the formula (Never) are hydrocarbon radicals having 1 to 6 carbon atoms, preferably aliphatic hydrocarbon radicals having 1 to 6 carbon atoms, preferably a methyl and / or an ethyl group.
  • A is numbers from 1 to 49, preferably 1 to 10
  • the radicals R 2 are groups - (- CH 2 -CH (R 13 ) -O-) n -R 6 -X (IIId), where at least one of the groups R 2 the rest X does not stand for H.
  • the radicals R 10 in the formula (IIId) are, independently of one another, a radical selected from the group of H, methyl or ethyl, where at least 20% of the radicals R 10 are H, preferably at least 50%.
  • the radicals, particularly preferably at least 80% of the radicals and particularly preferably all radicals R 10 are H. If several different radicals R 13 are present, these may be arranged randomly, alternately or in blocks.
  • X in formula (Nie) are preferably carboxyl groups -COOM, sulfonic acid groups -SO 3 M, sulfate groups -OSO 3 M.
  • these may be groups - (- CH 2 -CH (R 13 ) -O-) n -H in combination with groups - (- CH 2 -CH (R 13 ) -O-) n -SO 3 H act.
  • the radicals R 2 of the general formula include - (R 5 -O-) n -R 6 -X (III) radicals R 8 and / or R 9 . They may be radicals which comprise exclusively groups R 8 and / or R 9 , as well as those which additionally comprise groups R 7 in addition to R 8 and / or R 9 .
  • the formula (Never) is monomers R 7 and R 8 , where R 11 is H.
  • the radicals R 14 in the formula (Never) are, independently of one another, a radical selected from the group of H, methyl or ethyl, where at least 20% of the radicals R 10 are H, preferably at least 50%. the radicals, particularly preferably at least 80% of the radicals and particularly preferably all radicals R 14 are H.
  • R 6 in this embodiment is preferably a single bond and X is preferably H.
  • R 6 in this embodiment are derivatives of tris (2-hydroxyphenyl) methanes, which are obtainable by free-radical polymerizing carboxylic acid vinyl ester in the presence of compounds of general formulas (I) or (II).
  • the polymerization of carboxylic acid vinyl esters in the presence of polyalkoxy groups is known in principle to the person skilled in the art. In this reaction, vinyl ester, oligovinyl ester and / or polyvinyl ester groups are grafted onto the polyalkoxy groups, ie polyalkoxy groups having additional side groups are formed.
  • the polyvinyl ester groups are then at least partially hydrolyzed to OH groups.
  • the OH groups can then optionally be functionalized with groups -R 6 -X.
  • the reaction scheme is exemplified below.
  • Suitable carboxylic acid vinyl esters include in particular vinyl formate, vinyl acetate and vinyl propionate. Particularly suitable for modification are, in particular, compounds which have groups (IIIb) or (Never).
  • first tris (2-hydroxyphenyl) methane compounds of the general formulas (IV) or (V) with the desired substitution pattern with respect to R 1 , and R or R 3 and R 4 can be synthesized.
  • the tris (2-hydroxyphenyl) methane compounds of the general formulas (IV) or (V) can be alkoxylated in a second step in a manner known in principle.
  • the carrying out of alkoxylations is known in principle to the person skilled in the art. It is also known to the person skilled in the art that the reaction conditions, in particular the choice of catalyst, can influence the molecular weight distribution of the alkoxylates.
  • C 2 - to C 8 -alkylene oxides are used, for example, ethylene oxide, propylene oxide, butylene oxide or styrene oxide. Preference is given in each case to the 1, 2-alkylene oxides.
  • the use of these alkylene oxides leads to groups comprising R 7 radicals.
  • R 15 Glycidol (Via) or glycidol (Vlb) protected with a suitable protective group R 15 is used.
  • R 15 can be any type of group that can be used to protect the OH function during the alkoxylation. After the alkoxylation or even after the introduction of the groups -R 6 -X, they can be known in principle. cleaved way.
  • R 15 may be a t-butyl group or a benzyl group.
  • the alkoxylation may be a base-catalyzed alkoxylation.
  • the tris (2-hydroxyphenyl) methane compounds can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal such as sodium.
  • alkali metal hydroxides preferably potassium hydroxide or with alkali metal such as sodium.
  • the catalyst can be neutralized by the addition of acid (e.g., acetic acid or phosphoric acid) and filtered off as needed.
  • acid e.g., acetic acid or phosphoric acid
  • the catalyst can also be removed by adding commercially available silicates which are subsequently filtered off.
  • the alkoxylation can also be carried out in the presence of a solvent. This can e.g. Toluene, xylene, dimethylformamide or ethylene carbonate.
  • the alkoxylation can also be accelerated by the addition of crown ethers, for example by the addition of [18] -Kron-6.
  • the alkoxylation of the alcohols can also be carried out by other methods, for example by acid-catalyzed alkoxylation.
  • the acids can be protic acids or Lewis acids (such as, for example, BF 3. It is also possible to use, for example, double hydroxide clays as described in DE 43 25 237 A1, or double metal cyanide catalysts (DMC catalysts) can be used.
  • Suitable DMC catalysts are disclosed, for example, in DE-A 102 43 361, in particular in sections [0029] to [0041] and in the literature cited therein.
  • Zn-Co type catalysts can be used.
  • the alcohol R-OH may be admixed with the catalyst, the mixture dewatered as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture, and the catalyst can remain in the product due to this small amount.
  • the amount of catalyst can typically be less than 1000 ppm, for example 250 ppm and less.
  • the alkoxylation can alternatively be carried out by reaction of the compounds (IV) and (V) with cyclic carbonates such as ethylene carbonate.
  • Sulfate groups -OS0 3 M-containing derivatives can be obtained by reacting the terminal OH groups with S0 3 , sulfuric acid, chlorosulfuric acid or aminosulphonic acid (CAS No. 5329-14-6) and subsequent neutralization with, for example, sodium hydroxide solution. This can be done, for example, in a falling film reactor. By this reaction, only the terminal OH groups are substituted by sulfate groups. R 6 is a double bond in this reaction.
  • Sulfonate group -SO 3 M-containing derivatives can be obtained by substituting the OH group for Cl using phosgene or thionyl chloride.
  • the reaction can be carried out in the presence of a solvent such as chlorobenzene.
  • HCl liberated as well as liberated C0 2 or S0 2 can advantageously be removed from the system by stripping with nitrogen, so that ether cleavage is prevented.
  • the alkylalkoxychlor compound is then reacted with an aqueous solution of sodium sulphite, the chloride being substituted by sulphite and the sulphonate obtained.
  • the substitution can be carried out in the presence of a phase mediator (for example C 1 - to C 8 -alcohols) at a temperature of from 100 to 180 ° C. and under pressure.
  • a phase mediator for example C 1 - to C 8 -alcohols
  • the sulfonates may alternatively be obtained by adding vinylsulfonic acid to the compound (V) (or to VII or VIII, respectively). Details of this are described for example in EP-A 31 1 961.
  • Sulfonates can furthermore be obtained by reacting the compounds (V) (or else to VII or VIII) with 1,3-propane sultone or 1,4-butane sultone.
  • Derivatives comprising carboxylate groups -COOM can be obtained by oxidation of compound (V) (or also to VII or VIII, respectively).
  • all oxidizing agents are suitable, optionally in combination with suitable catalysts which can oxidize the terminal OH group of the compound (V) to the COOH group, without oxidizing other parts of the molecule to a great extent.
  • the oxidation may be carried out, for example, by means of air or oxygen using a noble metal catalyst (for example, a palladium-based catalyst).
  • Carboxylates can also be prepared by adding to the OH groups by means of a Michael addition of (meth) acrylic acid or a (meth) acrylic ester. If the esters are used, they are saponified after addition. Depending on whether acrylic acid or (meth) acrylic acid or its esters were used, terminal groups -CH 2 -CH 2 -COOM or -CH 2 -CH (CH 3 ) -COOM are obtained in this synthesis variant.
  • Carboxylate groups COOM can also be obtained by reacting the compounds (VII) or (VIII) with chloroacetic acid CICH 2 COOH or their salts CICH 2 COOM in the presence of a base.
  • Phosphate groups can be introduced by reaction with phosphorus pentoxide, phosphonate groups by reaction with vinylphosphonic acid.
  • Compounds having mono- or oligosaccharide groups can be prepared by converting the corresponding saccharide, for example glucose, into the corresponding butyl acetal with the aid of an acidic catalyst, such as, for example, para-toluenesulfonic acid and n-butanol.
  • an acidic catalyst such as, for example, para-toluenesulfonic acid and n-butanol.
  • the resulting water of reaction can be removed by applying a vacuum from the reaction mixture.
  • the compound (V) (or to VII or VIII) is added and propelled the Umacetalmaschine by distillative removal of butanol from the equilibrium.
  • the acidic catalyst can be neutralized at the end of the reaction by adding base, for example NaOH or KOH.
  • the compounds obtained have only one terminal group -R 6 -X or else several terminal and / or pendant groups -R 6 -X.
  • a linear group R 2 is formed which has terminally and / or laterally -R 6 -X groups. If, in an alternative synthesis, the protecting groups are not initially cleaved, but only the introduction of the groups -R 6 -X before, then only the terminal OH groups react. The cleavage of the protective groups can then take place. In this case, a group R 2 is formed which has a terminal group -R 6 -X and, in addition, pendant methylol groups -CH 2 OH.
  • At least one production well and at least one injection well are sunk into the crude oil deposit.
  • a deposit is provided with multiple injection wells and multiple production wells.
  • aqueous formulation of the described tris (2-hydroxyphenyl) methane derivative (I) is injected into the oil reservoir through the at least one injection well and oil is taken from the deposit through at least one production well.
  • the term "petroleum” in this context means not only pure phase oil, but the term also includes the usual crude oil-water emulsions.
  • the pressure generated by the pressed-in formulation, the oil flows in the direction of the production well and is about promoted the production well.
  • the deposit temperature of the crude oil deposit to which the process according to the invention is applied is from 10 to 150.degree. C., preferably from 10.degree. C. to 120.degree. C. and, for example, from 20.degree. C. to 70.degree.
  • an oil reservoir often has a uniform temperature in terms of time and area, except for thermal measures.
  • the stated reservoir temperature refers to the area of the reservoir between the injection and production wells, which is detected by the injected composition.
  • Methods for determining the temperature of a crude oil deposit are known in principle to the person skilled in the art. The temperature is usually made from temperature measurements at certain points of the formation.
  • the process according to the invention can be used in particular for oil reservoirs with an average permeability of 100 mD to 154 D, preferably 150 mD to 2 D and particularly preferably 200 mD to 1 D.
  • the permeability of a petroleum formation is given by the skilled person in the unit “Darcy” (abbreviated “D” or “mD” for “milli darcy”) and can be determined from the flow rate of a liquid phase in the petroleum formation depending on the applied pressure difference. The flow rate can be determined in core flood tests with formation cores.
  • the permeability in an oil reservoir need not be homogenous, but generally has a certain distribution, and accordingly, the permeability of a petroleum deposit is an average permeability.
  • an aqueous formulation which, in addition to water, comprises at least the described tris (2-hydroxyphenyl) -methane derivative (I). It is also possible to use mixtures of different tris (2-hydroxyphenyl) methane derivatives.
  • the formulation can be prepared in fresh water but also in salts containing water. These may be mixtures of different salts.
  • seawater can be used to prepare the aqueous formulation, or promoted formation water used in this manner can be used.
  • the formulation is usually applied in seawater.
  • the tris (2-hydroxyphenyl) methane derivative can advantageously be first dissolved in fresh water and the resulting solution diluted with formation water to the desired use concentration.
  • the formulation may preferably be prepared by pre-treating the water. sets, the tris (2-hydroxyphenyl) -methane derivative scattered as a powder and mixed with the water.
  • the salts may in particular be alkali metal salts and alkaline earth metal salts.
  • Examples of typical cations include Na + , K + , Mg 2+ or Ca 2+ and Mg 2+ .
  • Examples of typical anions include chloride, bromide, bicarbonate, sulfate or borate.
  • the formulation comprises salts
  • at least one or more alkali metal ions in particular at least Na +
  • alkaline earth metal ions may also be present, the weight ratio of alkali metal ions / alkaline earth metal ions generally being> 2, preferably> 3.
  • Suitable anions are usually at least one or more of halide ions, in particular at least CI "is available.
  • the amount of CI" at least 50 wt.%, Preferably at least 80 wt.% Relative to the total of all anions.
  • the total amount of all salts in the aqueous formulation is often from 10,000 ppm to 350,000 ppm (parts by weight) with respect to the sum of all components of the formulation.
  • the salinity is typically 20,000 ppm to 50,000 ppm and, if formation water is used, typically 100,000 ppm to 250,000 ppm.
  • the amount of alkaline earth metal ions may preferably be 1000 to 53,000 ppm.
  • the aqueous formulation may also include other components, such as. As biocides, stabilizers and inhibitors.
  • the concentration of the tris (2-hydroxyphenyl) methane derivative is determined so that the aqueous formulation has the desired viscosity for the application.
  • the viscosity of the formulation should generally be at least 3 mPas (measured at 25 ° C. and a shear rate of, for example, 7 s -1 , or as it preferably occurs in the reservoir), preferably at least 10 mPas.
  • the concentration of the tris (2-hydroxyphenyl) methane derivative in the formulation is from 0.01 to 10% by weight, often from 0.05 to 10% by weight, based on the sum of all components of the aqueous formulation.
  • the amount is 0.05 to 5 wt.%, Particularly preferably 0.05 to 1 wt.% And for example, about 0.1 wt.%.
  • Injecting the aqueous formulation may be done by conventional means.
  • the formulation can be injected by conventional pumps into one or more injection wells.
  • the injection wells are often lined with cemented steel pipes in the area of the oil reservoir, and the steel pipes are perforated at the desired location.
  • the formulation enters the petroleum formation through the perforation from the injection well.
  • the shear stress on entering the formation can be calculated by the person skilled in the art in a manner known in principle on the basis of the law of Hagen-Poiseuille using the area through which the formation flows, the mean pore radius and the volume flow.
  • the average permeability or porosity of the formation can be determined in a manner known in principle by measurements on cores. Naturally, the shear stress is greater the larger the volume flow of aqueous formulation injected into the formation.
  • the speed of the injection can be determined by the skilled person according to the properties of the formation (permeability, thickness) and the requirements of the oil field (number of injectors, their configuration, etc.).
  • the shear rate when entering the aqueous formulation into the formation is preferably at least 30,000 s -1 , preferably at least 60,000 s -1 and particularly preferably at least 90,000 s .
  • Tris (2-hydroxyphenyl) methane derivatives of the formula (I) which are particularly preferred for carrying out the process are the following components.
  • TRIS tris (3,5-di-hexy-f-butyl-2-hydroxyphenyl) -methane
  • TRIS [(- CH 2 -CH 2 -0) IIH] 3 TRIS [(- CH 2 -CH 2 -0) IIH] 2 [(CH 2 -CH 2 -0) ii-S0 3 Na]
  • TRIS [(CH 2 CH (CH 3 ) -O) 4 , 4 - (- CH 2 -CH 2 -O) i 3 H] 3 TRIS with 24 glycidol units and 9 EO units
  • the invention also relates to an aqueous formulation containing from 0.1 to 90% by weight of a tris (2-hydroxyphenyl) methane derivative from the above-mentioned. mentioned group, and containing 50 000 ppm to 350 000 ppm of inorganic salt, and (optionally) 0.01 to 5 wt.% Of at least one auxiliary component from the group of surfactants, antioxidants and biocides, and water and optionally other solvents.
  • the described derivatives (I) of tris (2-hydroxyphenyl) methane can be used to prepare various formulations for petroleum production as described above. Also particularly suitable are the TRIS derivatives which contain both EO units and glycidol units. Frequently used concentrations and other components:
  • Concentrations are often in the range of 0.01-10% by weight, often 0.05-10% by weight, preferred concentrations are between 0.1-1% by weight and particularly preferred concentrations between 0.1 and 0.5 wt .-%, each based on the total formulation.
  • Solvents can be used as further component. Typically, the derivative of tris (2-hydroxyphenyl) methane is dissolved in the formation water. Also a release in seawater is possible. Pre-dissolving with a water-miscible solvent, e.g. As ethanol or isopropanol for the preparation of concentrates with higher active content is possible. Well water can also be used.
  • C) Salts have an influence on the viscosity of the formulations. The target viscosity is often set below storage salinity by varying the concentration.
  • biocides are already used for the water treatment.
  • low-saline waters can be treated with algicides, fungicides, etc.
  • Tris (3,5-di-he / f-butyl-2-hydroxyphenyl) -methane (CAS No.143560-44-5) was prepared by the method described by MB Dinger, MJ Scott, Eur. J. Org. Chem. 2000, 2467 described method. Tris- (3,5-di-he / f-butyl-2-hydroxyphenyl) -methane is also abbreviated below as TRIS.
  • the product can also be prepared in the presence of crown ether [18] crown-6 as follows:
  • TRIS 80 g is suspended in toluene (220 ml) in a 2 l autoclave and treated with potassium tert-butylate (2.2 g) and crown ether [18] crown-6 (5.3 g).
  • TRIS [(- CH 2 -CH 2 -O) ii H] 3 synthesized in Example 1 .2 is dissolved in dichloromethane (45 g) and cooled to 5-10 ° C. Thereafter, chlorosulfonic acid (2, 12 g) is added dropwise so that the temperature does not exceed 10 ° C. The mixture is stirred for 1 h at 10 ° C, then overnight at room temperature, before the above reaction mixture in an aqueous NaOH solution (50%, 1, 98 g) at max. 10 ° C is dropped. The dichloromethane is removed under a slight vacuum on a rotary evaporator at 30-45 ° C. The product is characterized by 1 H-NMR and determines the water content of the solution (about 60%).
  • Volatile organic compounds are removed by a stream of nitrogen and the reactor is emptied.
  • the basic crude product is neutralized using commercially available Mg silicates, which are then filtered off.
  • the product is also characterized by 1 H NMR.
  • TRIS 50 g is suspended in toluene (100 g) in an autoclave and mixed with potassium heptafluate (1.7 g) and crown ether [18] crown-6 (4 g). It is rinsed three times with N 2 , a pre-pressure of about 1 .3 bar N 2 is set and the temperature is increased to 120 ° C. A mixture of glycidol (142 g) and ethylene oxide (31 .5 g) is metered in over a period of 8 hours so that the temperature remains at 120 ° C. The mixture is then stirred for 16 h at 80 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
  • the basic crude product is neutralized using commercially available Mg silicates, which are then filtered off.
  • the product is characterized by 1 H-NMR.
  • reaction mixture is heated to 120 ° C and benzyl glycidyl ether (CAS 2930-05-4, 17 g) is added over a period of 2 h, keeping the temperature at 120 ° C.
  • benzyl glycidyl ether CAS 2930-05-4, 17 g
  • the basic crude product is neutralized using commercially available Mg silicates, which are then filtered off.
  • 240 g of the benzyl-protected intermediate are obtained.
  • the resulting intermediate (200 g) is dissolved in a mixture of ethyl acetate (500 ml) and H 2 O (500 ml), palladium-on-charcoal (10%, 20 g) and 2.5 l autoclave transferred. It is rendered inert with N 2 three times and then hydrogen is metered in up to a pressure of 10 bar.
  • the reactor contents are heated to 80 ° C and held this reaction temperature for 20 h, wherein the hydrogen pressure is maintained at 10 bar.
  • the reactor is cooled to room temperature, decompressed, rendered inert with N 2 three times and emptied.
  • the heterogeneous catalyst is filtered off by means of a pressure filter under N 2 and organic solvents are removed on a rotary evaporator under vacuum at 80 ° C.
  • the product is also uniquely characterized by 1 H NMR.
  • TRIS 50 g is suspended in toluene (130 ml) in a 21 autoclave and combined with potassium heptafluate (1.4 g) and crown ether [18] crown-6 (3.3 g). It is rinsed three times with N 2 , a pre-pressure of about 1 .3 bar N 2 adjusted and the temperature increased to 130 ° C. Ethylene oxide (105 g) is metered in within 2 h, keeping the temperature at 130 ° C. The mixture is then stirred for 5 h at 130 ° C and then at 40 ° C overnight. Volatile organic compounds are removed by a stream of nitrogen and the reactor is emptied. The basic crude product is neutralized using commercially available Mg silicates, which are then filtered off.
  • the product is also characterized by 1 H NMR.
  • TRIS 25.2 g
  • toluene 46.4 g
  • potassium hepta-butoxide (0.84 g).
  • the intermediate (8.0 g) is dissolved in methanol (100 ml) and a solution of NaOMe in MeOH (30%, 1.8 g) is added. The solution thus obtained is stirred at room temperature overnight before the acidic ion exchanger Amberlite IRC86 (Fluka, 10 g) is added. The ion exchanger is then filtered off and the filtrate is concentrated by means of a rotary evaporator. The product is obtained in the form of a dark mass. MALDI-MS confirms glycosylation.
  • Example 2 Physical-chemical investigations
  • the viscosity measurements were carried out with a rheometer (Anton Paar MCR 301). For the viscosity measurements, aqueous solutions of the components were used.
  • demineralized water demineralized water
  • FIG. 1 shows the general shear profile of the synthesis examples according to the invention. It can be seen for 0.25 wt .-% solutions of TRIS [(- CH 2 -CH 2 -O) iiH] 3 (Synthesis Example 1 .2) at 25 ° C that the thickening effect (viscosity) not only in salt-free Solution (lower curve) but also under high-saline conditions (upper curve: reservoir water) is maintained under practice-relevant shear conditions.
  • FIG. 2 shows the temperature-dependent thickening (viscosity) from 25 ° to 80 ° C. under high-saline conditions (reservoir water) for three different tris (2-hydroxyphenyl) -methane derivatives (1% solutions each) at a constant shear rate of 7 s -1 : a) TRIS [(-CH 2 -CH 2 -O) 2- SO 3 Y] 3 (Synthesis Example 1, 4; curve below) b) TRIS [(CH 2 CH 2 -O) 9- ( -CH 2 COONa)] 3 (Synthesis Example 1.14, upper curve) c) TRIS [(CH 2 CH 2 -O) 9 ] 3 , degree of sulfation 50% (Synthesis Example 1 .16, in the middle curve).
  • FIG. 3 shows the temperature-dependent thickening (viscosity) from 25 ° to 80 ° C. under high-saline conditions (Bockstedt water) for two different tris (2-hydroxyphenyl) -methane derivatives (1% solutions in each case) in comparison with three known thickeners.
  • the polymeric thickeners Floopaam 3630S (from SNF) and Alcoflood 1285 Red (from BASF) and the quaternary ammonium salt cetyltrimethylammonium tosylate (CTAT, CAS 138-32-9 from Aldrich): a) TRIS [(CH 2 CH 2 - 0) 9 - (- CH 2 COONa)] 3 (Synthesis Example 1 .14 (1%) (line) b) Flopaam 3630S (1%) (lowest line, _._._._._._._. _.)
  • Figure 4 shows the temperature-dependent thickening (viscosity) of 25 ° to 80 ° C at a constant shear rate of 7 s "1 , under high saline conditions (reservoir water) for three different tris (2-hydroxyphenyl) methane derivatives (each 1% - Solutions):
  • FIG. 5 shows the stability of the micellar systems with TRIS [(- CH 2 -CH 2 -O) nH] 3 (Synthesis Example 1 .2) in saline water (93 g salt / liter, corresponds to 50% salinity of the reservoir). Water), water (0.1% solution of the thickener) against crude oil. The viscosities were determined at 25 ° C: a) Without contact with the crude oil (solid line)
  • FIG. 6 shows the properties (in Pa or Pas):
  • the surface tension of the surfactant in aqueous solution was determined using a conventional tensiometer. From the surface tension as a function of the surfactant concentration, the critical micelle formation concentration (cmc) was determined.
  • the critical micelle formation concentration in deionized water is 0.03 g / L (25 ° C).
  • the interfacial tension of an aqueous surfactant solution was determined to be hexadecane as the oil phase.
  • the table shows the interfacial tensions (mN / m) of 0.5% solutions of TRIS [(- CH 2 -CH 2 -O) n H] 3 (Synthesis Example 1 .2) in saline water (93 g salt / liter; % salinity of reservoir water) for crude oil from the Emlichheim deposit measured under the conditions specified.
  • the interfacial tension of the salty water against crude oil without additives is 14 mN / m at 23 ° C and 13 mN / m at 60 ° C.
  • triphenoxymethane derivatives of the invention are particularly suitable for deposits with extreme salinities (it has been tested, inter alia, to a salt content of about 200 g / l TDS) at moderately elevated temperatures up to 80 ° C. By reducing the salinity significantly higher temperature ranges are accessible. TriX is particularly well suited for Ca 2+ / Mg 2+ -containing deposits.
  • TriX As a viscoelastic surfactant system, TriX has a strong shear thinning and can therefore be pumped particularly well in the compositions according to the invention. Degradation due to strong shear is not observed. The possibility of ringing pumping is another advantage over polymer solutions. Chemical degradation is not observed.

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Abstract

L'invention concerne un procédé de récupération de pétrole permettant d'améliorer la récupération du pétrole. Selon ce procédé, on injecte une formulation aqueuse contenant du tris-(2-hydroxyphényl)-méthane de formule générale (I) dans un gisement pétrolifère par l'intermédiaire d'un puits d'injection et on extrait le pétrole brut du gisement par un puits de production. Dans la formule (I), les groupes R1, R2 et R ont les significations suivantes : les R représentent indépendamment les uns des autres 1 à 2 groupes hydrocarbures par cycle phényle, R1 représente de préférence H ou OH et les R2 représentent indépendamment les uns des autres des groupes de formule générale -(R5-O-)n-R6-X (III), où n est un nombre compris entre 1 et 50, les groupes R5 sont des groupes R7, R6 est une liaison simple ou un groupe alkylène ayant 1 à 10 atomes de carbone, X représente H ou un groupe terminal acide et R10 représente, par exemple, un groupe hydrocarbure C1-C6.
EP12775219.4A 2011-10-18 2012-10-12 Utilisation de dérivés de tris(2-hydroxyphényl)méthane pour la récupération tertiaire de pétrole Not-in-force EP2768924B1 (fr)

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EP12775219.4A EP2768924B1 (fr) 2011-10-18 2012-10-12 Utilisation de dérivés de tris(2-hydroxyphényl)méthane pour la récupération tertiaire de pétrole
PCT/EP2012/070245 WO2013057044A1 (fr) 2011-10-18 2012-10-12 Utilisation de dérivés de tris(2-hydroxyphényl)méthane pour la récupération tertiaire de pétrole

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Families Citing this family (3)

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WO2014064151A1 (fr) 2012-10-23 2014-05-01 Basf Se Sels d'ammonium quaternisés d'époxydes hydrocarbyliques et utilisation desdits sels d'ammonium quaternisés d'époxydes hydrocarbyliques comme additifs de carburants et de lubrifiants
WO2014139935A1 (fr) 2013-03-11 2014-09-18 Basf Se Utilisation de polyalcoxylates dans des compositions lubrifiantes
CN105008318A (zh) 2013-03-13 2015-10-28 温特沙尔控股有限公司 制备取代三(2-羟基苯基)甲烷的方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61136577A (ja) * 1984-12-06 1986-06-24 Lion Corp 石油回収用流体
DE3735056A1 (de) * 1987-10-16 1989-04-27 Basf Ag Verfahren zur herstellung von ether- und polyglykolethersulfonaten und nach diesem verfahren hergestellte produkte
TW289763B (fr) 1992-11-11 1996-11-01 Ciba Geigy Ag
DE4325237A1 (de) 1993-07-28 1995-02-02 Basf Ag Verfahren zur Herstellung von Alkoxylierungsprodukten in Gegenwart von mit Additiven modifizierten Mischhydroxiden
US8785355B2 (en) 2001-02-13 2014-07-22 Schlumberger Technology Corporation Viscoelastic compositions
GB2408506B (en) 2003-11-29 2007-06-13 Schlumberger Holdings Anionic viscoelastic surfactant
MXPA04010535A (es) 2002-04-26 2005-01-25 Basf Ag Mezclas de alcoxilato y detergentes que contienen las mismas.
DE10243361A1 (de) 2002-09-18 2004-04-01 Basf Ag Alkoxylatgemische und diese enthaltende Waschmittel
US7053127B1 (en) 2002-09-16 2006-05-30 Nalco Company Quaternized amido cyclic amine surfactant
US7320952B2 (en) 2004-01-21 2008-01-22 Schlumberger Technology Corporation Additive for viscoelastic fluid
US7125825B2 (en) 2003-04-25 2006-10-24 Tomah Products, Inc. Amidoamine salt-based viscosifying agents and methods of use
KR20060134968A (ko) * 2004-01-19 2006-12-28 미츠비시 가스 가가쿠 가부시키가이샤 신규한 트리페닐메탄 유도체, 그것을 함유하는 유기겔화제, 유기 겔 및 유기 섬유
US7373977B1 (en) 2004-03-29 2008-05-20 Oil Chem Technologies Process for oil recovery employing surfactant gels
US7772164B2 (en) 2004-06-02 2010-08-10 Rhodia, Inc. Multicomponent viscoelastic surfactant fluid and method of using as a fracturing fluid
US20060084579A1 (en) 2004-10-15 2006-04-20 Berger Paul D Viscoelastic surfactant mixtures
US7279446B2 (en) 2004-11-15 2007-10-09 Rhodia Inc. Viscoelastic surfactant fluids having enhanced shear recovery, rheology and stability performance
US20060183646A1 (en) 2005-02-15 2006-08-17 Halliburton Energy Services, Inc. Viscoelastic surfactant fluids and associated methods
US7461694B2 (en) 2005-11-16 2008-12-09 Rhodia Inc. Methods for recovering oil from an oil reservoir
KR20090066161A (ko) 2007-12-18 2009-06-23 주식회사 동진쎄미켐 감광성 화합물 및 이를 포함하는 포토레지스트 조성물
US8618321B2 (en) * 2010-05-20 2013-12-31 Basf Se Derivatives of tris(2-hydroxyphenyl)methane, their preparation and use
EP2571923B1 (fr) * 2010-05-20 2014-12-17 Basf Se Dérivés de tris(2-hydroxyphényl)méthane, leur production et leur utilisation

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MX2014004523A (es) 2014-09-08
US9212545B2 (en) 2015-12-15
MX360810B (es) 2018-11-16
BR112014009480A2 (pt) 2017-05-09
CN104024368B (zh) 2017-10-13
EP2768924B1 (fr) 2017-12-13
CN104024368A (zh) 2014-09-03
EA201490813A1 (ru) 2014-09-30
US20130098609A1 (en) 2013-04-25
WO2013057044A1 (fr) 2013-04-25
EA028823B1 (ru) 2018-01-31
CA2851326A1 (fr) 2013-04-25
EA028823B9 (ru) 2018-08-31

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